Hydrocarbon distillate containing boron ester of polyalkyl-polyhydroxyalkyl-alkylenepolyamine

ABSTRACT

HYDROCARBON DISTILLATES ARE BENEFITED BY THE ADDITION THERETO OF A BORON ESTER OF A POLYALKYL-POLYHYDROXYALKYLALKYLENEPOLYAMINE. AS A SPECIFIC EXAMPLE, THE COMBUSTION PROPERTIES OF GASOINE IS IMPROVED.

United States Patent O1 ice Patented Feb. 2, 1971 3,560,386 HYDROCARBON DISTILLATE CONTAINING BORON ESTER OF POLYALKYL-POLYHY- DROXYALKYL-ALKYLENEPOLYAMINE Henryk A. Cyba, Evanston, Ill., assignor to Universal Oil Products Company, Des Plaines, Ill., a corporation of Delaware No Drawing. This application is a continuation-in-part of application Ser. No. 559,410, June 22, 1966, which is a division of application Ser. No. 366,921, May 12, 1964. This application Dec. 26, 1968, Ser. No. 787,203

Int. Cl. C10n1 7/02 U.S. Cl. 252-49.6 6 Claims ABSTRACT OF THE DISCLOSURE Hydrocarbon distillates are benefited by the addition thereto of a boron ester of a polyalkyl-polyhydroxyalkylalkylenepolyamine. As a specific example, the combustion properties of gasoine is improved.

CROSS REFERENCE TO RELATED APPLICATIONS This is a continuation-in-part of application Ser. No. 559,410, filed June 22, 1966 (now U.S. Pat. No. 3,445,422 issued May 20, 1969, which is turn is a division of application Ser. No. 366,921, filed May 12, 1964, now U.S. Pat. No. 3,301,888 issued Jan. 31, 1967.

DESCRIPTION OF THE INVENTION Boron compounds are used as additives in hydrocarbon distillates and particularly in gasoline to improve the combustion or burning properties of the gasoline. The novel boron compounds of the present invention may be similarly used to effect such improvement in combustion properties. Furthermore, the novel compounds of the present invention also will serve as an inhibitor to stabilize the gasoline against deterioration in storage and transpor tation due to oxidation, polymerization and/ or other undesired reactions, thus inhibiting the formation of sediment in the gasoline, dispersion of sediment if formed, preventing discoloration, preventing decrease in antiknock properties of the gasoline etc.

The combustion properties of kerosene and fuel oil also can be similarly improved by the novel compounds of the present invention. The improvement in the burning qualities of the kerosene or fuel oil results in cleaner burning of the oil. In addition, the kerosene and the fuel oil is stabilized against oxidation, polymerization and other undesired reactions, and is improved in substantially the same manner as hereinbefore described. When used in lubricating oil the addition serves to maintain the lubricity properties of the oil and avoids undesired deteroration caused by oxidation, heat, polymerization or other undesired reactions.

The additive of the present invention is a boron ester of a particular polyalkyl-polyhydroxyalkyl-alkylenepolyamine which is illustrated by the following formula:

where R is an alkyl group of from 4 to about 50 carbon atoms, R is an alkylene group of from 2 to about 6 carbon atoms, R" is an alkylene group of from 2 to about 6 carbon atoms and n is an integer of from to 4.

From the above formula, it will be seen that it is es sential that each nitrogen atom contains a hydroxyalkyl group attached thereto and that the terminal nitrogen atoms each contain an alkyl radical attached thereto.

Referring to the formula hereinbefore set forth, when n is zero, the compound is an N,N'-dialkyl-N-hydroxyalkyl-aminoalkyl-alkanolamine, which also may be named N,N dialkyl-N,N-dihydroxyalkyl-alkylenediamine. The alkyl groups preferably are secondary alkyl groups and contain from 4 to about carbon atoms each and more particularly from 4 to 20 carbon atoms each. Illustrative preferred compounds in this embodiment include:

N,N-di-sec-butyl-N-hydroxyethyl-aminoethyl-ethanolamine, N,N'-di-sec-pentyl-N-hydroxyethyl-aminoethyl-ethanolamine, N,N'-di-sec-hexyl-N-hydroxyethyl-aminoethyl-ethanolamine, N,N'-di-sec-octyl-N-hydroxyethylaminoethyl-ethanolamine, N,N-di-sec-nonyl-N-hydroxyethyl-aminoethyl-ethanolamine, N,N'-di-sec-decyl-N-hydroXyethyl-aminoethyl-ethanolamine, N,N'-di-sec-undecyl-N-hydroxyethyl-aminoethyl-ethanolamine, N,N-di-sec-dodecyl-N-hydroxyethyl-aminoethyl-ethanolamine, N,N'-di-sec-tridecyl-N-hydroxyethyl-aminoethyl-ethanolamine, N,N-di-sec-tetradecyl-N-hydroxyethyl-aminoethylethanolamine, N,N'-di-sec-pentadecyl-N-hydroxyethyl-aminoethylethanolamine, N,N'-di-sec-hexadecyl-N-hydroxyethy1-aminoethyl ethanolamine, N,N-di-sec-heptadecyl-N-hydroxyethyl-aminoethylethanolamine, N,N-di-sec-octadecyl-N-hydroxyethyl-aminoethylethanolamine, N,N-di-sec-nonadecyl-N-hydroxyethyl-aminoethylethanolamine, N,N'-di-sec-eicosyl-N-hydroxyethyl-aminoethyl-ethanolamine, etc.

The above compounds are illustrative of compounds in which R and R" each contain two carbon atoms. It is understood that corresponding compounds are included in which one or both of the groups containing two carbon atoms are replaced by a group containing 3, 4, 5 or 6 carbon atoms.

Referring again to the above formula, when n is 1, the compounds of the present invention are named N,N-bis- [N-alkyl-N-(hydroxyalkyl) aminoalkyl] alkanolamine which also can be named N ,N -dialkyl-N ,N ,N -tri-(hydroxyalkyl)-diethylenetriamine. Here again, it will be noted that each terminal nitrogen contains an alkyl group and each nitrogen atom contains a hydroxyalkyl group attached thereto. Illustrative preferred compounds in this embodiment include:

N,N-bis[N-sec-butyl-N- (2-hydroxyethyl) -aminoethyl] etha nolarnine,

N,N-bis- [N-sec-pentyl-N-(Z-hydroxyethyl) -aminoethyl] ethanolamine,

N,N-bis- [N-sec-hexyl-N- (2-hydroxyethyl -aminoethyl] ethanolamine,

N,N-bis- [N-sec-heptyl-N- (Z-hydroxyethyl) -aminoethyl] ethanolamine,

N,N-bis- [N-sec-octyl-N- (2-hydroxyethyl -aminoethyl] ethanolamine,

N,N-bis- [N-sec-nonyl-N- (2-hydroxyethyl) -aminoethyl] ethanolamine,

N,N-bis [N-sec-decyl-N- 2-hydroxyethyl -aminoethyl] ethanolamine,

are secondary alkyl groups. In another embodiment, these groups may be cycloalkyl groups and particularly cyclohexyl, alkylcyclohexyl, dialkylcyclohexyl, etc., although they may comprise cyclobutyl, cyclopentyl, cycloheptyl, cyclooctyl, etc., and alkylated derivatives thereof. The cycloalkyl groups may be considered as corresponding to secondary alkyl groups. The secondary alkyl configuration is definitely preferred although, when desired, the alkyl groups attached to the terminal nitrogen atoms may be normal alkyl groups but not necessarily with equivalent results.

The polyalkyl polyhydroxyalkyl-alkylenepolyamine is prepared by \first reductively alkylating an alkylenepolyamine and then subjecting the resultant alkylenepolyamine containing alkyl groups attached to the terminal nitrogen atoms to oxyalkylenation. Accordingly, the oxyalkylenation is performed on alkylenepolyamines containing only secondary nitrogen atoms. There are no primary nitrogen atoms available and, therefore, will not result in the formation of a nitrogen atom containing two hydroxyalkyl groups.

The alkylenepolyamines to be subjected to reductive alkylation include ethylenediamine, diethylenetriamine, triethylenetetramine, tetraethylenepentamine, pentaethylenehexamine and corresponding alkylenepolyamines in which the ethylene group or groups are replaced by propylene, butylene, pentylene and/or hexylene groups. In order to prepare the preferred compounds in which the alkyl groups are of secondary alkyl groups, the reductive alkylation is effected using a ketone. Any suitable ketone may be used and will be selected to produce the desired secondary alkyl groups to be attached to the terminal nitrogen atoms. Illustrative preferred ketones include: methyl ethyl, ketone, methyl propyl ketone, methyl butyl ketone, methyl pentyl ketone, methyl hexyl ketone, methyl heptyl ketone, methyl octyl ketone, methyl nonyl ketone, methyl decyl ketone, methyl undecyl ketone, methyl dodecyl ketone, methyl tridecyl ketone, methyl tetradecyl ketone, methyl pentadecyl ketone, methyl hexadecyl ketone, methyl heptadecyl ketone, methyl octadecyl ketone, etc., diethyl ketone, ethyl propyl ketone, ethyl butyl ketone, ethyl pentyl ketone, ethyl hexyl ketone, ethyl heptyl ketone, ethyl octyl ketone, ethyl nonyl ketone, ethyl decyl ketone, ethyl undecyl ketone, ethyl dodecyl ketone, ethyl tridecyl ketone, ethyl tetradecyl ketone, ethyl pentadecyl ketone, ethyl hexadecyl ketone, ethyl heptadecyl ketone, etc., dipropyl ketone, propyl butyl ketone, propyl pentyl ketone, propyl hexyl ketone, propyl heptyl ketone, propyl octyl ketone, propyl nonyl ketone, propyl decyl ketone, propyl undecyl ketone, propyl dodecyl ketone, propyl tridecyl ketone, propyl tetradecyl ketone, propyl, pentadecyl ketone, propyl hexadecyl ketone, etc., dibutyl ketone, butyl pentyl ketone, butyl hexyl ketone, butyl heptyl ketone, butyl octyl ketone, butyl nonyl ketone, butyl decyl ketone, butyl undecyl ketone, butyl dodecyl ketone, butyl tridecyl ketone, butyl tetradecyl ketone, butyl pentadecyl ketone, etc., dipentyl ketone, pentyl hexyl ketone, pentyl heptyl ketone, pentyl octyl ketone, pentyl nonyl ketone, pentyl decyl ketone, pentyl undecyl ketone, pentyl dodecyl ketone, pentyl tridecyl ketone, pentyl tetradecyl ketone, etc., dihexyl ketone, hexyl heptyl ketone, hexyl octyl ketone, hexyl nonyl ketone, hexyl decyl ketone, hexyl undecyl ketone, hexyl dodecyl ketone, hexyl tridecyl ketone, etc., diheptyl ketone, heptyl octyl ketone, heptyl nonyl ketone, heptyl decyl ketone, heptyl undecyl ketone, heptyl dodecyl ketone, etc., dioctyl ketone, octyl nonyl ketone, octyl decyl ketone, octyl undecyl ketone, etc., dinonyl ketone, nonyl decyl ketone, didecyl ketone, etc. It is understood that the ketones may be of straight or branched chain configuration. Ketones are available commercially or they may be synthesized as required. A number of ketones and particularly the higher boiling ketones are available as mixtures which are either products or byproducts of commercial operations. These mixtures generally are available at comparatively low cost and, as another advantage of the present invention, the mixtures may be used without the added time and expense of separating specific compounds in pure state. One such mixture available commercially is Stearone which is diheptadecyl ketone.

The reductive alkylation of the ketone and alkylenepolyamine is effected in any suitable manner. The reaction is effected using at least two moles of ketone per mole of alkylenepolyamine and generally an excess of the ketone, which may range up to about twenty mole proportions of ketone per one mole proportion of alkylenepolyamine, is employed to insure complete reaction. In one embodiment the reaction is effected in the presence of hydrogen and a suitable reductive alkylation catalyst in one step, which may be either continuous or batch type operation. Any suitable reductive alkylation catalyst is employed including those containing nickel, platinum, palladium, etc., preferably composited with a suitable support. A particularly preferred catalyst comprises a composite of platinum and alumina, which may or may not contain combined halogen. The platinum generally is present in the catalyst in a concentration of from about 0.1 to about 2% by weightof the final catalyst and the halogen, when present, is in a concentration of total halogen of from about 0.01% to about 1% by weight of the final catalyst, the halogen preferably comprising fluorine and/or chlorine. Another suitable catalyst comprises an intimate mixture of copper oxide, chromium oxide and barium oxide. When using the platinum catalyst, the temperature generally will be within the range of from about to about 260 C. and a hydrogen pressure of from about to about 3,000 pounds per square inch or more.

In a continuous type operation, the catalyst is disposed as a fixed bed in a reaction zone and the alkylenepolyamine, ketone and hydrogen, at the required temperature and pressure, are passed through the catalyst in either upward or downward flow. The reactor effluent is separated into a hydrogen stream and unreacted products, all or part of which may be recycled to the reaction zone, and the desired terminally alkylated alkylenepolyamine is separated from other high boiling products, if any. In a batch type operation, the alkylenepolyamine, ketone and catalyst are disposed in a reaction zone which is pressured with hydrogen and then heated to the desired temperature. After cooling, the products are separated to recover the desired terminally alkylated alkylenepolyamine. While the one-step process generally is preferred, it is understood that the reaction may be effected in two steps. In the first step, effected in the absence of hydrogen, the Schiifs base is first prepared and then is hydrogenated in a separate step to form the desired terminally alkylated alkylenepolyamine.

The terminally alkylated alkylenepolyamine, prepared in the above manner, then is subjected to oxyalkylenation. The oxyalkylenation is readily effected by charging the terminally alkylated alkylenepolyamine into a reaction zone and passing alkylene oxide, particularly ethylene oxide, into contact with the alkylenepolyamine, The alkylene oxide will be used in a proportion of at least one mole thereof per each nitrogen atom in the alkylenepolyamine. For example, when N,N'-dialkyl-ethylenediamine is to be oxyalkylenated, at least two moles of alkylene oxide are used per mole of ethylenediamine. Usually an excess of the alkylene oxide is employed in order to insure complete reaction. This reaction readily occurs at a low temperature which may range from room temperature to C. in the absence of a catalyst. As hereinbefore set forth, ethylene oxide is preferred. Other alkylene oxides include propylene oxide, butylene oxide, pentylene oxide, hexylene oxide, etc., as well as styrene oxide, epichlorohydrin, etc. It is understood that the R" alkylene group may be substituted by such groups as phenyl, alkoxy, thio-oxy, halo, hydroxy, etc. It will be noted that the alkylated alkylenepolyamine contains only secondary nitrogen atoms and accordingly the oxyalkylenation will result in each nitrogen atom containing only one oxyalkylene group.

The polyalkyl polyhydroxyalkyl alkylenepolyamine, prepared in the above manner, is reacted with a borylating agent. Any suitable borylating agent may be used. A particularly preferred borylating agent is boric acid. Other borylating agents include trialkyl borates in which the alkyl groups preferably contain from 1 to 4 carbon atoms each. In the use of the latter type borylating agent, the reaction is effected by transesterification and, accordingly, there is no advantage to using trialkyl borates containing more than 4 carbon atoms in each alkyl group, although the higher boiling trialkyl borates may be used when satisfactory and advantages appear therefor. Still other borylating agents include alkyl boric acid, dialkyl boric acid, boric oxide, boric acid complex, cycloalkyl boric acid, aryl boric acid, dicycloalkyl boric acid, diaryl boric acid or substitution products of these with alkoxy, alkyl and/or halo groups, etc. In another embodiment the boryating agent is a bornate of the formula RB(OH) and, in still another embodiment, it is a borinate of the formula R B-OH, where R is hydrogen, alkyl, aryl or cycloalkyl. When R is alkyl, it preferably contains from one to carbon atoms. When R is aryl, it preferably is phenyl, although it may be naphthyl, anthracyl, etc. When R is cycloalkyl, it preferably is cyclohexyl, although it may be cyclopropyl, cyclobutyl, cyclopentyl, cycloheptyl, cyclooctyl, cyclononyl, cyclodecyl, cycloundencyl, cyclododecyl, etc. Also it is understood that the aryl or cycloalkyl nucleus may be substituted with alkoxy, alkyl or halo groups, etc.

The reaction of the borylating agent and polyalkylpolyhydroxyalkyl-alkylenepolyamine is effected in any suitable manner. The ortho-borates are formed by heating and stirring the reactants at a temperature up to about 100 C. and thus within the range of from about 60 to about 100 C. when using boric acid. The meta-borates are formed at temperatures above about 100 C. and thus may be within the range of from about 100 to about 200 C. or more. The higher temperature of from about 100 to about 200 C. is used when employing trialkyl borate in order to effect the transesterification reaction. In one method the reactants are refluxed in the presence of a solvent. Any suitable solvent may be used and advantageously comprises an aromatic hydrodrocarbon solvent including benzene, toluene, xylene, eth ylbenzene, cumene, etc., n-hexane, n-heptane, n-octane, chlorinate hydrocarbons, etc., or mixtures thereof. The use of a solvent is particularly preferred when boric acid is used as the borylating agent. When using a trialkyl borate as the borylating agent, the solvent may be omitted. While no catalyst normally is required, a catalyst may be used when employing the trialkyl borate. Any suitable catalyst may be employed including sodium hydrogen sulfate, potassium hydrogen sulfate, tin, oxide, polyalkyl tin derivatives, alkoxy tin derivatives, polyalkyl titanium derivatives, alkoxy titanium derivatives, trialkyl or trialkoxy aluminum, etc. The borylating agent and polyalkyl polyhydroxyalkyl-alkylenepolyamine generally are used in a mole proportion within range of from about 0.5 to 2 mole proportions of borylating agent per one mole proportion of polyalkylpolyhydroxyalkyl-alkylenepolyamine.

In another embodiment, an alcohol, including aliphatic or aromatic alcohol or mercaptan including aliphatic or aromatic mercaptan, is included in the reaction charge to satisfy one or two of the valences of the boron. When used, the alcohol or mercaptain is employed in an amount of from about 0.5 to 2 mole proportion thereof per one mole proportion of the .polyalkyl-plyhydrxyalkyl-alkylenepolyamine. Preferred aliphatic alcohols include methanol, isopropanal, butanol, sec-butyl alcohol, pentanol, hexanol, heptanol, octanol, nonanol, decanol, undecanol,

dodecanol, tridecanol, tetradecanol, pentadecanol, hexadecanol, heptadeconal, octadecanol, nonadecanol, eicosa- 1101, etc. Preferred aromatic alcohols include phenol, cresol, xylenol, etc. The alcohol or aromatic phenol moiety may be substituted lWith alkoxy groups or thioalkoxy groups. Preferred mercaptans include butyl mercaptan, pentyl mercaptan, hexyl mercaptan, heptyl mercaptan, octyl mercaptan, nonyl mercaptan, decyl mercaptan, undecyl mercaptan, dodecyl mercaptan, etc., and thiophenol, thiocresol, thioxylenol, etc.

As hereinbefore set forth, the reaction is readily effected by refluxing the borylating agent and polyalkyl-polyhydroxyalkyl-alkylenepolyamine, with or without solvent and/or catalyst as required. Refiuxing is continued until the required amount of water when using boric acid or alcohol when using trialkyl borate is collected. Following completion of the reaction, the solvent and alcohol, if any, are removed by vacuum distillation. The borated polyalkyl-polyhydroxyalkyl-alkylenepolyamine, is recovered as a liquid and used as such or, when desired, the product may be retained in the solvent and used as such or the product may be prepared as a solution in a different solvent and used in this manner.

As hereinbefore set forth, the exact composition of the product has not been established. When the polyalkyl-polyhydroxyalkyl alkylenepolyamine is a polyalkylpolyhydroxy-alkyl-ethylenediamine, probably compounds may include one or more of the following as monomer or recurring units:

(2) a cyclic configuration in which each of the oxygens of the hydroxyl group are attached to a boron atom and the third valence is otherwise satisfied, (3) a polycyclic structure similar to that described in (2) joined by the BOB linkage, (4) compound in which each of the hydrogens of the hydroxyl groups are replaced with a (5) compounds having boroxine configuration and (6) metaborates.

Because of the uncertainty as to the actual composition of the product, these products are being claimed generically and by their method of manufacture.

From the above description, it will be seen that a number of diflFerent compounds are included within the scope of the present invention, but that all of these products are boron esters of compounds of specific chemical configuration, in which the terminal nitrogen atoms are each substituted with an alkyl group and each nitrogen atom is substituted with a hydroxyalkyl group. It is understood that the different compounds are not necessarily equivalent in their activity or use for the same or different purposes and that a mixture of the different compounds may be used in the present invention.

As hereinbefore set forth the compounds of the present invention are used as additives in hydrocarbon distillates. Illustrative hydrocarbon distillates include gasoline, naphtha, kerosene, jet fuel, solvents, fuel oil, burner oil, range oil, diesel oil, marine oil, turbine oil cutting oil, rolling oil, soluble oil, drawing oil, sloshing oil, lubricating oil, fingerprint remover, etc. As hereinbefore set forth, in the oils, the compounds of the present invention serve to inhibit oxidative deterioration, thermal deterioration, polymerization, etc., thereby retarding and/or pre- 9 venting sediment formation, dispersion of sediment when formed, preventing and/or retarding discoloration, rust or corrosion inhibitor, detergent, antifouling additives, etc. In addition the compounds are active as microbicides, algaecides, etc.

It is understood that the compounds of the present invention may be used in conjunction with other additives. For example, they may be used in admixture with a phenolic antioxidant, including particularly 2,6-ditertiarybutyl-4-methylphenol. Other phenolic antioxidant include 2,4-dimethyl-6-tertiary-butyl phenol, tertiarybutyl catechol, etc. Other additives may be of the amine type including aniline, phenylenediamine and particularly N,N'-di-sec-alkyl-phenylenediamine such as N,N'-di-isopropyl-p-phenylenediamine, N,N-di-iso-propyl-o-phenylenediamine, N,N'-di-sec-butyl-p-phenylenediamine, N,N- di-sec-butyl o phenylenediamine, N,N-di-sec-amyl-pphenylene diamine, N,N'-di-sec-amyl o phenylenediamine, N,N-di sec hexyl-p-phenylenediamine, N,N'-disec-hexyl o phenylenediamine, N,N-di-sec-heptyl-pphenylenediamine, N,N-di sec heytyl-o-phenylenediamine, N,N-di-sec-octyl p phenylenediamine, N,N-disec-nonyl-p-phenylenediamine, N,N di sec nonyl-ophenylenediamine, N,N'-di-sec-decyl-p-phenylenediamine, N,N'-di-sec-decyl-o-phenylenediamine, etc. Still other additives may include antiknock agents, particularly tetraethyl lead, dye, metal deactivator and particularly disalicylal-diaminopropane, additional corrosion inhibitor, etc. The additional inhibitor may be used in a concentration of from about one percent to about 70 percent by weight of the compound of the present invention. The additional inhibitor may be used in a concentration within the range of from about 0.0001% to about 0.5% and more particularly from about 0.001% to about 0.1% by weight of the substrate.

The compound of the present invention will be used in a stabilizing concentration, which will depend upon the particular substrate. The concentration may be within the range of from about 0.000'1% to about 0.5% by weight, although higher concentrations up to 10% by weight may be used, particularly in lubricating oil. When the additive is added to a liquid, it is incorporated in the hydrocarbon distillate with intimate stirring in order to insure uniform distribution therein.

The additive of the present invention may be utilized as such or prepared as a solution in a suitable solvent including alcohols and particularly methanol, ethanol, propanol, butanol, etc., hydrocarbons and particularly benzene, toluene, xylene, cumene, decalin, etc.

The following examples are introduced to illustrate further the novelty and utility of the present invention but not with the intention of unduly limiting the same.

Example I The compound of this example was prepared by reacting 1 mole proportion of boric acid with 1 mole proportion of N,N di-sec-octyl-N,N'-di-(Z-hydroxyethyl)- ethylenediamine and 1 mole proportion of isodecyl alcohol. The N,N'-di-sec-octyl-N,N di (2-hydroxyethyl)- ethylenediamine was prepared by reacting N,N-bis-( 1- methylheptyl)-ethylenediamine with 2 mole proportions of ethylene oxide. The oxyethylenation was eflected by intimately mixing the reactants in a turbomixer at a temperature of about 115 C. and a pressure of about 250 psi for about two hours. The product was recovered as a liquid boiling at 188 C. at 0.4 mm. Hg and having an index of refraction 11 of 1.4705, basic nitrogen content of 5.37 meq./g., hydroxyl content of 4.5 meq./g. and a G.L.C. purity of 98%.

The borylation was effected by heating and refluxing a mixture of 107.5 g. (0.25 mole) of the N,N-di-secoctyl-N,N'-di-(2-hydroxyethyl)ethylenediamine, 39.5 g. (0.25 mole) of isodecyl alcohol, 15.45 g. (0.25 mole) of boric acid and 200 g. of benzene solvent. A total of 13.5 cc. of water was collected. The benzene solvent was re- 10 moved by distillating at 175 C. under a vacuum of 18 mm. Hg. The product was recovered as a liquid having a basic nitrogen of 3.86 meg/g. and a percent boron of 1.85% by Weight.

Example II The compound of this example was prepared by reacting tri-n-butyl borate with N,N-di-sec-octyl-N,N-di-(2- hydroxyethyl)-ethylenediamine. The latter compound was prepared in substantially the same manner as described in Example I. This is a transesterification reaction and was eflected by heating and refluxing 37.2 g. (0.1 mole) of N,N-di-sec-octyl-N,N'-di-(2-hydroxyethyl) ethylenediamine and 45.8 g. (0.2 mole) of tri-n-butyl borate. No solvent was employed in this preparation and the temperature of reaction ranged from to C. A total of 27 g. of butanol fraction was collected, the butanol resulting from the transesterification reaction. Following completion of the reaction, the reaction mixture was distilled at 170 C. under a vacuum of 18 mm, Hg. The borated product was recovered as a liquid having a boron content of 2.81 weight percent. This corresponds to the theoretical boron content of 3.16% by weight of a compound in which each hydroxyl group of the N,N'-di-secoctyl-N,N-di-( 2 hydroxyethyl) ethylenediamine undergoes transesterification reaction with separate tributyl borate molecules to form a compound in which each of the boron atoms is attached to two butoxy radicals and to one ethoxy radical of the N,N'-di-sec-octyl-N,N-di-(2- hydroxyethyl)-ethylenediamine. As hereinbefore set forth, the formation of this compound has not been definitely established. Example III The compound of this example is prepared by the reaction of equal mole proportions of N ,N -di-sec-octyl- N ,N ,N -tri (2 hydroxyethyl) diethylenetriamine and boric acid. The N ,N -di-sec-octyl-N ,N ,N -tri-(Z-hydroxyethyl)-diethylenetriamine is prepared by reacting 1 mole proportion of N ,N -bis-(1-ethy1-3-methylpentyl)-diethylenetriamine with 3 mole proportions of ethylene oxide in a turbomixer at a temperature of about 100 C. for about 4 hours. N ,N -di-sec-octyl-N ,N ,N -tri-(2-hydroxyethyl)-diethylenetriamine is recovered as a light colored liquid having a boiling point of 233-235 C. at 0.5 mm. Hg, a basic nitrogen content of 6.58 meq./g. and a hydroxyl content by acetylation method of 5.75 meg/g.

The reaction of the N ,N -di-sec-0ctyl-N ,N ,N -tri-(2- hydroxyethyl)-diethylenetriamine and boric acid is effected by heating and refluxing the mixture in the presence of benzene solvent until the theoretical amount of water is collected. Following completion of the reaction, the reaction product is distilled under vacuum to remove benzene solvent and to recover the borylated product as a liquid.

Example IV The compound of this example is prepared by reacting equal mole proportions of boric acid and N ,N -di-secpentatriacontyl-N ,N ,N -tri- (Z-hydroxyethyl) -diethylene triamine under refluxing conditions at a temperature of 134 C. in the presence of xylene solvent. The heating and refluxing is continued until the desired amount of water is collected indicating the formation of metaboric acid derivative or formation of boroxine, and the product is recovered as a solution in the xylene solvent.

Example V The compound of this example is prepared by heating and refluxing a mixture of 1 mole proportion of boric acid, 1 mole proportion of N,N'-di-sec-butyl-N,N'-di'(2- hydroxypropyl)-ethylenediamine and 1 mole proportion of butyl mercaptan in the presence of benzene solvent. The heating and refluxing is continued until the reaction is completed and the product then is subjected to vacuum distillation to remove the benzene solvent. The product is recovered as a liquid and may be used as such or formed as a solution in a suitable solvent,

Example VI The compound of Example I is used in a concentration of 0.3% by weight as an additive in gasoline and serves to improve the combustion characteristics of the gasoline, as well as serving as an antistatic agent therein. In addition the additive serves as an inhibitor against oxidation, polymerization and other-undesired reactions.

Example VII The compound of Example II is used in the concentration of 0.01% by weight as an additive in kerosene to improve the burning qualities thereof and to retard sediment formation, as well as to disperse any sediment which may have formed in the kerosene.

Example VIII The compound of this example is prepared by reacting equal mole proportions of N,N'-di-sec-octyl-N,N-di.-(2- hydroxyethyl)-ethylenediamine and nonyl boronic acid. The reaction is effected in substantially the same manner as hereinbefore set forth. The resulting boronate is used as an additive in a concentration of by Weight in lubricating oil and serves to inhibit deterioration of the lubricity properties of the oil.

Example IX The compound of this example is prepared by reacting one mole proportion of N ,N -di-sec-butyl-N ,N ,N -tri- (Z-hydroxyethyl)-diethylenetriamine with 2 mole proportions of phenyl butyl borinic acid. The reaction is effected in substantially the same manner as hereinbefore described.

The borinate prepared in the above manner is used in a concentration of 0.001% by Weight as an additive in fuel oil to retard deterioration of the fuel oil.

Example X In this example the borate of Example I was evaluated in commercial fuel oils to determine the sludge dispersing and inhibiting properties.

1 Plus 6.4 p.p.m. of a commercial copper deactivator.

The data indicate that the borate possesses color stabilizing properties and deposit reducing properties.

I claim as my invention:

1. Hydrocarbon distillate containing from about 0.000l% to about 10% by weight of a boron ester of a polyalkylpolyhydroxyalkyl-alkylenepolyamine of the formula:

where R is an alkyl group of from 4 to about carbon atoms, R is an alkylene group of from 2 to about 6 carbon atoms, R" is an alkylene group of from 2 to about 6 carbon atoms and n is an integer of from 0 to 4.

2. The composition of claim 1 wherein said boron ester is a borate of N,N'-di-sec-alkyl-N,N-di-(hydroxyalkyl) -ethylenediamine.

3. The hydrocarbon distillate of claim 1 being gasoline.

4. The hydrocarbon distillate of claim 1 being kerosene.

5. The hydrocarbon distillate of claim 1 being fuel oil.

6. The hydrocarbon distillate of claim 1 being lubricating oil.

References Cited UNITED STATES PATENTS 3,311,653 3/1967 DeGray et al. 4472 3,325,261 6/1967 Knowles et al. 4472 3,325,262 6/1967 DeGray et a1. 4472 DANIEL E. WYMAN, Primary Examiner Y. H. SMITH, Assistant Examiner us. 01. X.R. 4472 

